Kinetics of adsorption on activated carbon: application of heterogeneous vacancy solution theory

The kinetics of single component adsorption on activated carbon is investigated here using a heterogeneous vacancy solution theory (VST) of adsorption. The adsorption isotherm is developed to account for the adsorbate non-ideality due to the size difference between the adsorbate molecule and the vacant site, while incorporating adsorbent heterogeneity through a pore-width-related potential energy. The transport process in the bidisperse carbon considers coupled mass transfer in both macropore and micropore phases simultaneously. Adsorbate diffusion in the micropore network is modeled through effective medium theory, thus considering pore network connectivity in the adsorbent, with the activation energy for adsorbate diffusion related to the adsorption energy, represented by the Steele 10-4-3 potential for carbons. Experimental data of five hydrocarbons, CO2 and SO2 on Ajax carbon at multiple temperatures, as well as three hydrocarbons on Norit carbon at three temperatures are first fitted by the heterogeneous VST model to obtain the isotherm parameters, followed by application of the kinetic model to uptake data on carbon particles of different sizes and geometry at various temperatures. For the hydrocarbons studied, the model can successfully correlate the experimental data for both adsorption equilibrium and kinetics. However, there is some deviation in the fit of the desorption kinetics for polar compounds such as CO2 and SO2, due to the inadequacy of the L-J potential model in this case. The significance of viscous transport in the micropores is also considered here and found to be negligible, consistent with recent molecular simulation studies. (C) 2002 Elsevier Science Ltd. All rights reserved.

Vacancy solution theory for binary adsorption equilibria in heterogeneous carbon

A heterogeneous modified vacancy solution model of adsorption developed is evaluated. The new model considers the adsorption process through a mass-action law and is thermodynamically consistent, while maintaining the simplicity in calculation of multicomponent adsorption equilibria, as in the original vacancy solution theory. It incorporates the adsorbent heterogeneity through a pore-width-related potential energy, represented by Steele's 10-4-3 potential expression. The experimental data of various hydrocarbons, CO2 and SO2 on four different activated carbons - Ajax, Norit, Nuxit, and BPL - at multiple temperatures over a wide range of pressures were studied by the heterogeneous modified VST model to obtain the isotherm parameters and micropore-size distribution of carbons. The model successfully correlates the single-component adsorption equilibrium data for all compounds studied on various carbons. The fitting results for the vacancy occupancy parameter are consistent with the pressure change on different carbons, and the effect of pore heterogeneity is important in adsorption at elevated pressure. It predicts binary adsorption equilibria better than the IAST scheme, reflecting the significance of molecular size nonideality.

Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state

A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption systems. (C) 2002 Elsevier Science (USA).

Modeling of gas adsorption equilibrium over a wide range of pressure: A thermodynamic approach based on equation of state

A thermodynamic approach based on the Bender equation of state is suggested for the analysis of supercritical gas adsorption on activated carbons at high pressure. The approach accounts for the equality of the chemical potential in the adsorbed phase and that in the corresponding bulk phase and the distribution of elements of the adsorption volume (EAV) over the potential energy for gas-solid interaction. This scheme is extended to subcritical fluid adsorption and takes into account the phase transition in EAV The method is adapted to gravimetric measurements of mass excess adsorption and has been applied to the adsorption of argon, nitrogen, methane, ethane, carbon dioxide, and helium on activated carbon Norit R I in the temperature range from 25 to 70 C. The distribution function of adsorption volume elements over potentials exhibits overlapping peaks and is consistently reproduced for different gases. It was found that the distribution function changes weakly with temperature, which was confirmed by its comparison with the distribution function obtained by the same method using nitrogen adsorption isotherm at 77 K. It was shown that parameters such as pore volume and skeleton density can be determined directly from adsorption measurements, while the conventional approach of helium expansion at room temperature can lead to erroneous results due to the adsorption of helium in small pores of activated carbon. The approach is a convenient tool for analysis and correlation of excess adsorption isotherms over a wide range of pressure and temperature. This approach can be readily extended to the analysis of multicomponent adsorption systems. (C) 2002 Elsevier Science (USA).

Sistema de accionamento de pás móveis para turbina de impulso

A actual dependência mundial dos combustíveis fósseis e a crescente necessidade de redução do seu consumo têm culminado em novas directrizes de gestão de recursos de energia. A utilização de recursos energéticos renováveis apresenta-se como um caminho vital para o desenvolvimento sustentável da nossa sociedade. Assim sendo, a energia das ondas surge como potencial fonte de energia que muitos autores afirmam como sendo um dos sectores com maior potencial energético por metro quadrado de área. Contudo, esta ainda é uma tecnologia muito recente, que ainda evidencia uma grande diversidade de conceitos e que ainda se encontra numa fase inicial de demonstração. É neste contexto que foi criado o projecto CORES que visa desenvolver uma turbina de impulso com pás guia de posição variável, no âmbito do desenvolvimento de novos dispositivos e componentes para produção de energia através das ondas do mar. Neste trabalho será desenvolvido um sistema de accionamento de pás móveis para a turbina de impulso, tendo como principal objectivo o fabrico de um protótipo. Assim sendo, será realizado o desenvolvimento, dimensionamento e análise dos seus elementos móveis, bem como do sistema de actuação que melhor se adeqúe e permita um correcto funcionamento do conjunto.

Automatic learning for the classification of chemical reactions and in statistical thermodynamics

This Thesis describes the application of automatic learning methods for a) the classification of organic and metabolic reactions, and b) the mapping of Potential Energy Surfaces(PES). The classification of reactions was approached with two distinct methodologies: a representation of chemical reactions based on NMR data, and a representation of chemical reactions from the reaction equation based on the physico-chemical and topological features of chemical bonds. NMR-based classification of photochemical and enzymatic reactions. Photochemical and metabolic reactions were classified by Kohonen Self-Organizing Maps (Kohonen SOMs) and Random Forests (RFs) taking as input the difference between the 1H NMR spectra of the products and the reactants. The development of such a representation can be applied in automatic analysis of changes in the 1H NMR spectrum of a mixture and their interpretation in terms of the chemical reactions taking place. Examples of possible applications are the monitoring of reaction processes, evaluation of the stability of chemicals, or even the interpretation of metabonomic data. A Kohonen SOM trained with a data set of metabolic reactions catalysed by transferases was able to correctly classify 75% of an independent test set in terms of the EC number subclass. Random Forests improved the correct predictions to 79%. With photochemical reactions classified into 7 groups, an independent test set was classified with 86-93% accuracy. The data set of photochemical reactions was also used to simulate mixtures with two reactions occurring simultaneously. Kohonen SOMs and Feed-Forward Neural Networks (FFNNs) were trained to classify the reactions occurring in a mixture based on the 1H NMR spectra of the products and reactants. Kohonen SOMs allowed the correct assignment of 53-63% of the mixtures (in a test set). Counter-Propagation Neural Networks (CPNNs) gave origin to similar results. The use of supervised learning techniques allowed an improvement in the results. They were improved to 77% of correct assignments when an ensemble of ten FFNNs were used and to 80% when Random Forests were used. This study was performed with NMR data simulated from the molecular structure by the SPINUS program. In the design of one test set, simulated data was combined with experimental data. The results support the proposal of linking databases of chemical reactions to experimental or simulated NMR data for automatic classification of reactions and mixtures of reactions. Genome-scale classification of enzymatic reactions from their reaction equation. The MOLMAP descriptor relies on a Kohonen SOM that defines types of bonds on the basis of their physico-chemical and topological properties. The MOLMAP descriptor of a molecule represents the types of bonds available in that molecule. The MOLMAP descriptor of a reaction is defined as the difference between the MOLMAPs of the products and the reactants, and numerically encodes the pattern of bonds that are broken, changed, and made during a chemical reaction. The automatic perception of chemical similarities between metabolic reactions is required for a variety of applications ranging from the computer validation of classification systems, genome-scale reconstruction (or comparison) of metabolic pathways, to the classification of enzymatic mechanisms. Catalytic functions of proteins are generally described by the EC numbers that are simultaneously employed as identifiers of reactions, enzymes, and enzyme genes, thus linking metabolic and genomic information. Different methods should be available to automatically compare metabolic reactions and for the automatic assignment of EC numbers to reactions still not officially classified. In this study, the genome-scale data set of enzymatic reactions available in the KEGG database was encoded by the MOLMAP descriptors, and was submitted to Kohonen SOMs to compare the resulting map with the official EC number classification, to explore the possibility of predicting EC numbers from the reaction equation, and to assess the internal consistency of the EC classification at the class level. A general agreement with the EC classification was observed, i.e. a relationship between the similarity of MOLMAPs and the similarity of EC numbers. At the same time, MOLMAPs were able to discriminate between EC sub-subclasses. EC numbers could be assigned at the class, subclass, and sub-subclass levels with accuracies up to 92%, 80%, and 70% for independent test sets. The correspondence between chemical similarity of metabolic reactions and their MOLMAP descriptors was applied to the identification of a number of reactions mapped into the same neuron but belonging to different EC classes, which demonstrated the ability of the MOLMAP/SOM approach to verify the internal consistency of classifications in databases of metabolic reactions. RFs were also used to assign the four levels of the EC hierarchy from the reaction equation. EC numbers were correctly assigned in 95%, 90%, 85% and 86% of the cases (for independent test sets) at the class, subclass, sub-subclass and full EC number level,respectively. Experiments for the classification of reactions from the main reactants and products were performed with RFs - EC numbers were assigned at the class, subclass and sub-subclass level with accuracies of 78%, 74% and 63%, respectively. In the course of the experiments with metabolic reactions we suggested that the MOLMAP / SOM concept could be extended to the representation of other levels of metabolic information such as metabolic pathways. Following the MOLMAP idea, the pattern of neurons activated by the reactions of a metabolic pathway is a representation of the reactions involved in that pathway - a descriptor of the metabolic pathway. This reasoning enabled the comparison of different pathways, the automatic classification of pathways, and a classification of organisms based on their biochemical machinery. The three levels of classification (from bonds to metabolic pathways) allowed to map and perceive chemical similarities between metabolic pathways even for pathways of different types of metabolism and pathways that do not share similarities in terms of EC numbers. Mapping of PES by neural networks (NNs). In a first series of experiments, ensembles of Feed-Forward NNs (EnsFFNNs) and Associative Neural Networks (ASNNs) were trained to reproduce PES represented by the Lennard-Jones (LJ) analytical potential function. The accuracy of the method was assessed by comparing the results of molecular dynamics simulations (thermal, structural, and dynamic properties) obtained from the NNs-PES and from the LJ function. The results indicated that for LJ-type potentials, NNs can be trained to generate accurate PES to be used in molecular simulations. EnsFFNNs and ASNNs gave better results than single FFNNs. A remarkable ability of the NNs models to interpolate between distant curves and accurately reproduce potentials to be used in molecular simulations is shown. The purpose of the first study was to systematically analyse the accuracy of different NNs. Our main motivation, however, is reflected in the next study: the mapping of multidimensional PES by NNs to simulate, by Molecular Dynamics or Monte Carlo, the adsorption and self-assembly of solvated organic molecules on noble-metal electrodes. Indeed, for such complex and heterogeneous systems the development of suitable analytical functions that fit quantum mechanical interaction energies is a non-trivial or even impossible task. The data consisted of energy values, from Density Functional Theory (DFT) calculations, at different distances, for several molecular orientations and three electrode adsorption sites. The results indicate that NNs require a data set large enough to cover well the diversity of possible interaction sites, distances, and orientations. NNs trained with such data sets can perform equally well or even better than analytical functions. Therefore, they can be used in molecular simulations, particularly for the ethanol/Au (111) interface which is the case studied in the present Thesis. Once properly trained, the networks are able to produce, as output, any required number of energy points for accurate interpolations.

Maximização da valorização energética em aterros sanitários recorrendo a equipamentos baseados no Ciclo Orgânico de Rankine (ORC)

Atualmente, os aterros sanitários representam uma solução para a gestão e tratamento dos resíduos sólidos urbanos. Da deposição, ocorrem duas formas de emissões ao longo do tempo, a produção de biogás e de lixiviados, que resultam sobretudo da decomposição da matéria orgânica. Um dos principais constituintes do biogás é o metano, o qual tem elevado poder calorífico. O presente trabalho aborda, a maximização da valorização energética em aterros sanitários, recorrendo a equipamentos baseados no Ciclo Orgânico de Rankine (ORC) para a produção de eletricidade. É apresentado como caso de estudo a central de valorização energética da Suldouro, em Sermonde, que produz eletricidade a partir do biogás resultante da decomposição da matéria orgânica depositada em aterro. O biogás é utilizado como combustível para os motogeradores utilizados para o seu aproveitamento energético, sendo que apenas cerca de 40% do potencial energético contido no biogás é transformado em eletricidade, registando-se perdas sobretudo nas emissões dos gases de exaustão e na água de arrefecimento dos motores. Para avaliação do potencial da recuperação energética dos gases de escape é avaliado o desempenho termodinâmico do ciclo ORC. Para tal foi desenvolvida uma ferramenta em MATLAB utilizando como modelo a configuração do ORC com recuperador de calor. O cálculo das propriedades termodinâmicas dos fluidos foi obtido através da criação de uma sub-rotina que chama o programa CoolProp. Este programa restitui propriedades como a entalpia, entropia, pressões e temperaturas em cada ponto do ciclo, permitindo assim ao utilizador otimizar o tempo na obtenção de resultados. A avaliação económica é fundamental na tomada de decisões por parte do investidor e dos financiadores do projeto. É então apresentada a análise económica e efetuada uma análise de sensibilidade, onde foram efetuadas variações nos vetores mais importantes de forma a poder avaliar-se o impacto em termos da sua rentabilidade. A ferramenta desenvolvida permite obter de forma prática, os três indicadores económicos extremamente influentes no que se refere à tomada de decisão. A utilização dos sistemas ORC e os seus benefícios não se esgotam na maximização dos aproveitamentos da valorização energética em aterros sanitários. Também a recuperação de calor para a produção de energia elétrica pode ter um impacto importante em muitos setores intensivos de energia, contribuindo significativamente para a redução do consumo e aumentando a eficiência de todo o processo de produção.

Melhoria da eficiência energética nos ascensores: a recuperação de energia

A presente tese descreve diferentes soluções que permitem a reutilização da energia recuperada em ascensores eléctricos de roda de aderência dotados de conversores electrónicos de frequência e dessa forma contribuir para a melhoria da eficiência energética nos ascensores. Nos ascensores, a energia potencial é constantemente transferida enquanto a cabina está em movimento. Se a cabina se estiver a movimentar em sentido descendente com plena carga, ou em sentido ascendente, mas vazia, o motor estará em modo gerador. Quando a cabina se movimenta em sentido descendente, e o peso na cabina é superior ao peso do contrapeso, então o binário do motor encontra-se em sentido contrário à velocidade, isto é, o motor está a travar, havendo lugar à recuperação de energia. Igualmente, se a cabina subir vazia, também se poderá recuperar energia eléctrica. A energia acumulada em forma de energia potencial nas pessoas e no contrapeso pode ser recuperada, dado que o motor estará a funcionar como um gerador. De modo a estudar a viabilidade técnica e económica das diferentes soluções foram realizadas medições a uma amostra representativa de ascensores eléctricos de roda de aderência. Esta amostra é constituída por 39 ascensores que estão instalados em diferentes tipos de edifícios e que pertencem a diferentes categorias de utilização, de acordo com a norma VDI 4707:2009. Para cada ascensor foi medida a energia consumida e a energia gerada para uma manobra completa – a descida e a subida da cabina sem carga. A partir das medições, e com base na norma VDI 4707:2009 foram calculados os valores anualizados de energia eléctrica consumidos e produzidos por cada ascensor. A partir das 5 hipóteses identificadas para a utilização da energia recuperada (carregamento de bateria para alimentação dos circuitos em stand-by; carregamento de supercondensador para alimentação dos circuitos em stand-by; carregamento de supercondensador para alimentar o barramento DC; reinjecção da energia no barramento DC de um conjunto de ascensores em grupo; reinjecção da energia na rede eléctrica do edifício onde o ascensor está instalado) foi realizada a avaliação técnica e a avaliação económico-financeira para cada um dos ascensores. Por último, foi desenvolvido um simulador que permite definir a solução de recuperação de energia que seja técnica e economicamente mais viável, para um dado ascensor eléctrico de roda de aderência instalado, mediante a introdução dos parâmetros técnicos do ascensor em avaliação.

A Multiple Criteria Utility-based Approa h for the Unit Commitment with Wind Power and Pumped Storage Hydro

The integration of wind power in eletricity generation brings new challenges to unit commitment due to the random nature of wind speed. For this particular optimisation problem, wind uncertainty has been handled in practice by means of conservative stochastic scenario-based optimisation models, or through additional operating reserve settings. However, generation companies may have different attitudes towards operating costs, load curtailment, or waste of wind energy, when considering the risk caused by wind power variability. Therefore, alternative and possibly more adequate approaches should be explored. This work is divided in two main parts. Firstly we survey the main formulations presented in the literature for the integration of wind power in the unit commitment problem (UCP) and present an alternative model for the wind-thermal unit commitment. We make use of the utility theory concepts to develop a multi-criteria stochastic model. The objectives considered are the minimisation of costs, load curtailment and waste of wind energy. Those are represented by individual utility functions and aggregated in a single additive utility function. This last function is adequately linearised leading to a mixed-integer linear program (MILP) model that can be tackled by general-purpose solvers in order to find the most preferred solution. In the second part we discuss the integration of pumped-storage hydro (PSH) units in the UCP with large wind penetration. Those units can provide extra flexibility by using wind energy to pump and store water in the form of potential energy that can be generated after during peak load periods. PSH units are added to the first model, yielding a MILP model with wind-hydro-thermal coordination. Results showed that the proposed methodology is able to reflect the risk profiles of decision makers for both models. By including PSH units, the results are significantly improved.

Influência dos equipamentos de aquecimento, arrefecimento e AQS na certificação energética de edifícios

Na União Europeia os sectores dos transportes e da indústria são ambos grandes consumidores de energia, mas são os edifícios residenciais e de serviços onde o consumo energético é maior, e em 2005, segundo a EnerBuilding, representavam cerca de 17% dos consumos de energia primária em termos nacionais. A energia gasta com a iluminação, o aquecimento, o arrefecimento e AQS das habitações, locais de trabalho e locais de lazer é superior à consumida pelos sectores dos transportes e da indústria. As habitações representam dois terços do consumo total de energia dos edifícios europeus, o qual aumenta todos os anos com a melhoria da qualidade de vida, traduzindo-se numa maior utilização dos sistemas de climatização. Neste sentido, e de acordo com o decreto-lei que transpõe para a legislação portuguesa a diretiva comunitária relativa ao desempenho energético dos edifícios, todos os Estados da União Europeia devem ter um sistema de certificação energética para informar o cidadão sobre a qualidade térmica dos edifícios, aquando da construção, da venda ou do arrendamento. Assim, entrou em vigor em Portugal, desde 1 de Janeiro de 2009, a obrigatoriedade de apresentação de um certificado de eficiência energética, no ato de compra, venda ou aluguer de edifícios novos e existentes. A certificação energética permite assim aos futuros utilizadores dos edifícios obter informação sobre os potenciais consumos de energia, no caso dos novos edifícios ou no caso de edifícios existentes sujeitos a grandes intervenções de reabilitação, dos seus consumos reais ou aferidos para padrões de utilização típicos, passando o consumo energético a integrar um conjunto dos aspetos importantes para a caracterização de qualquer edifício. Em edifícios de serviços, o certificado energético assegura aos utentes do edifício ou da fração que este reúne condições para garantir a eficiência energética e a adequada qualidade do ar interior. Uma vez que passamos 80% do nosso tempo em edifícios, e que isto se reflete num consumo cada vez mais elevado do sector residencial e dos serviços no consumo total energético do país, este trabalho pretende fazer a comparação dos vários equipamentos de aquecimento, de arrefecimento e de AQS e qual a influência dos mesmos na certificação energética de edifícios, e consequentemente na eficiência dos mesmos, sendo que a eficiência e a certificação energética de um edifício deve ser um aspeto relevante a levar em consideração no momento do planeamento ou da construção, bem como na aquisição de uma nova habitação. Um projeto concebido de modo a tirar proveito das condições climáticas, da orientação solar, dos ventos dominantes e utilizadas técnicas construtivas e os materiais adequados, é possível reduzir os gastos energéticos com a iluminação ou os sistemas de climatização.

Control in distribution networks with demand side management

The way in which electricity networks operate is going through a period of significant change. Renewable generation technologies are having a growing presence and increasing penetrations of generation that are being connected at distribution level. Unfortunately, a renewable energy source is most of the time intermittent and needs to be forecasted. Current trends in Smart grids foresee the accommodation of a variety of distributed generation sources including intermittent renewable sources. It is also expected that smart grids will include demand management resources, widespread communications and control technologies required to use demand response are needed to help the maintenance in supply-demand balance in electricity systems. Consequently, smart household appliances with controllable loads will be likely a common presence in our homes. Thus, new control techniques are requested to manage the loads and achieve all the potential energy present in intermittent energy sources. This thesis is focused on the development of a demand side management control method in a distributed network, aiming the creation of greater flexibility in demand and better ease the integration of renewable technologies. In particular, this work presents a novel multi-agent model-based predictive control method to manage distributed energy systems from the demand side, in presence of limited energy sources with fluctuating output and with energy storage in house-hold or car batteries. Specifically, here is presented a solution for thermal comfort which manages a limited shared energy resource via a demand side management perspective, using an integrated approach which also involves a power price auction and an appliance loads allocation scheme. The control is applied individually to a set of Thermal Control Areas, demand units, where the objective is to minimize the energy usage and not exceed the limited and shared energy resource, while simultaneously indoor temperatures are maintained within a comfort frame. Thermal Control Areas are overall thermodynamically connected in the distributed environment and also coupled by energy related constraints. The energy split is performed based on a fixed sequential order established from a previous completed auction wherein the bids are made by each Thermal Control Area, acting as demand side management agents, based on the daily energy price. The developed solutions are explained with algorithms and are applied to different scenarios, being the results explanatory of the benefits of the proposed approaches.

Rényi entropy and the thermodynamic stability of black holes

Thermodynamic stability of black holes, described by the Rényi formula as equilibrium compatible entropy function, is investigated. It is shown that within this approach, asymptotically flat, Schwarzschild black holes can be in stable equilibrium with thermal radiation at a fixed temperature. This implies that the canonical ensemble exists just like in anti-de Sitter space, and nonextensive effects can stabilize the black holes in a very similar way as it is done by the gravitational potential of an anti-de Sitter space. Furthermore, it is also shown that a Hawking–Page-like black hole phase transition occurs at a critical temperature which depends on the q-parameter of the Rényi formula.

The financial sustainability of passive house construction in Ireland.

In Ireland the average energy cost for a household in 2006 was estimated to be €1,767, an increase of 4% on 2005 figures. With the state o f the current economic climate, home owners are beginning to realise the potential of energy efficient construction methods. The Passive House Standard offers a cost efficient and sustainable construction solution compared to the Traditional Irish construction methods. This report focuses on the Cost comparison between Passive House construction and traditional construction methods. The report also focuses on barriers that are slowing market penetration of the Passive House standard in the Irish Market. It also identifies potential energy savings that passive house occupants would benefit from. The report also highlights professional opinions on the future development o f the Passive House Standard in Ireland. The conclusions of this report are that the Passive House Standard is a more financially suitable construction solution compared to that o f a traditional dwelling complying with the Irish Building Regulations. The report also concludes that the Passive House Standard won’t be introduced as an Irish Building Regulation in the future but that it will have a big impact on future building regulations. The hypothesis o f this report is supported by data obtained from a literature review, qualitative data analysis and a case study. The report recommends that in order for the Passive House Standard to penetrate further into the Irish construction market, various barriers must be rectified. Local manufactures must start producing suitable components that suit the Passive House specification. The Building Energy Rating system must be altered in order for the Passive House to achieve its potential BER rating.

Rethinking economy-wide rebound measures: an unbiased proposal

In spite of having been first introduced in the last half of the ninetieth century, the debate about the possible rebound effects from energy efficiency improvements is still an open question in the economic literature. This paper contributes to the existing research on this issue proposing an unbiased measure for economy-wide rebound effects. The novelty of this economy-wide rebound measure stems from the fact that not only actual energy savings but also potential energy savings are quantified under general equilibrium conditions. Our findings indicate that the use of engineering savings instead of general equilibrium potential savings downward biases economy-wide rebound effects and upward-biases backfire effects. The discrepancies between the traditional indicator and our proposed measure are analysed in the context of the Spanish economy.

NO rebinding to myoglobin: a reactive molecular dynamics study.

The rebinding of NO to myoglobin after photolysis is studied using the 'reactive molecular dynamics' method. In this approach the energy of the system is evaluated on two potential energy surfaces that include the heme-ligand interactions which change between liganded and unliganded myoglobin. This makes it possible to take into account in a simple way, the high dimensionality of the transition seam connecting the reactant and product states. The dynamics of the dissociated NO molecules are examined, and the geometrical and energetic properties of the transition seam are studied. Analysis of the frequency of recrossing shows that the height of the effective rebinding barrier is dependent on the time after photodissociation. This effect is due mainly to protein relaxation and may contribute to the experimentally observed non-exponential rebinding rate of NO, as has been suggested previously.